Amine-containing acyclic hydrofluoroethers and methods of using the same

ABSTRACT

An acyclic fluorinated compound of formula (I) is amine-containing acyclic hydrofluoroethers. The acyclic fluorinated compound is useful as heat transfer, solvent cleaning, fire extinguishing agents and electrolyte solvents and additives.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing under 35 U.S.C. 371 ofPCT/US2017/018780, filed Feb. 22, 2017, which claims the benefit of U.S.Application No. 62/306947, filed Mar. 11, 2016, the disclosure of whichis incorporated by reference in its/their entirety herein.

TECHNICAL FIELD

The present disclosure relates to amine-containing acyclichydrofluoroethers and methods of using the same.

SUMMARY

There continues to be a need for inert fluorinated fluids which have lowglobal warming potential while providing high thermal stability, lowtoxicity, nonflammability, good solvency, and a wide operatingtemperature range to meet the requirements of various applications.Those applications include, but are not restricted to, heat transfer,solvent cleaning, fire extinguishing agents, and electrolyte solventsand additives.

In one aspect, an acyclic fluorinated compound of the general formula(I) is disclosed

where:

X is selected from F or CF₃, and Y is selected from H, F or CF₃, whereinwhen X is CF₃ then Y is F and when Y is CF₃ then X is F;

each R_(f) ¹ is independently selected from a linear or branchedperfluorinated alkyl group comprising 1-8 carbon atoms and optionallycomprising at least one catenated atom selected from O, N, orcombinations thereof; or the two R_(f) ¹ groups are bonded together toform a fluorinated ring structure comprising 4-8 carbon atoms andoptionally comprising at least one catenated atom selected from O, N, orcombinations thereof;

each R_(h) is independently H or CH₃;

A is selected from F or CF₃;

Z is selected from H, F, or CF₃and

Q is selected from (i) a F atom, (ii) a Cl atom, (iii) a linear, cyclic,or branched perfluorinated alkyl group comprising 1-8 carbon atoms andoptionally comprising at least one catenated atom selected from O, N, orcombinations thereof, or (iv) a G(R_(f) ²)_(e) group, where G is an Oatom or a N atom wherein:

when Q is a Cl atom, then Z and A are F atoms;

when G is O then e is 1, Z is H, F, or CF₃; A is F; and R_(f) ² is alinear or branched perfluorinated alkyl group comprising 1-10 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof;

when G is N then e is 2, and each R_(f) ² group is independently alinear or branched perfluorinated alkyl group comprising 1-8 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof or the two R_(f) ² groups are bondedtogether to form a fluorinated ring structure comprising 4-8 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof with the proviso that when A is CF₃then Z is F, and when Z is CF₃ then A is F.

The above summary is not intended to describe each embodiment. Thedetails of one or more embodiments of the invention are also set forthin the description below. Other features, objects, and advantages willbe apparent from the description and from the claims.

DETAILED DESCRIPTION

As used herein, the term

“a”, “an”, and “the” are used interchangeably and mean one or more; and

“and/or” is used to indicate one or both stated cases may occur, forexample A and/or B includes, (A and B) and (A or B);

“alkyl” refers to a monovalent group that is a radical of an alkane,which is a saturated hydrocarbon. The alkyl group can be linear,branched, cyclic or combinations thereof;

“catenated” means an atom other than carbon (for example, oxygen ornitrogen) that is bonded to at least two carbon atoms in a carbon chain(linear or branched or within a ring) so as to form acarbon-heteroatom-carbon linkage; and

“perfluorinated” means a group or a compound wherein all hydrogen atomsin the C—H bonds have been replaced by C—F bonds.

As used herein, a chemical structure that depicts the letter “F” in thecenter of a ring indicates that all unmarked bonds of the ring arefluorine atoms.

Also herein, recitation of ranges by endpoints includes all numberssubsumed within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75,9.98, etc.).

Also herein, recitation of “at least one” includes all numbers of oneand greater (e.g., at least 2, at least 4, at least 6, at least 8, atleast 10, at least 25, at least 50, at least 100, etc.).

Heat transfer fluids may be used to transmit heat from one location toanother, for example, to prevent over heating of a device or to maintainprecise temperature control or for energy conversion, as in the captureof waste heat and the conversion to electrical or mechanical energy.Presently, various fluids are used for heat transfer. The suitability ofthe heat transfer fluid depends upon the application process. Forexample, in some electronic applications, a heat-transfer fluid which isinert, has low toxicity, good environmental properties, and good heattransfer properties over a wide temperature range is desirable.

Vapor phase soldering is a process application that requires heattransfer fluids which are especially suitable for high temperatureexposure. In such application, temperatures of between 170° C. and 250°C. are typically used with 200° C. being particularly useful forsoldering applications using a lead based solder and 230° C. useful forthe higher melting lead free solders. Currently, the heat transferfluids used in this application are of the perfluoropolyether (PFPE)class. While many PFPEs have adequate thermal stability at thetemperatures employed, they also possess the notable drawback of beingenvironmentally persistent with extremely long atmospheric lifetimeswhich, in turn, gives rise to high global warming potentials (GWPs). Assuch, there is a need for new materials which possess thecharacteristics of the PFPEs that make them useful in vapor phasesoldering as well as in other high temperature heat transferapplications (e.g., chemical inertness, thermal stability and effectiveheat transfer, liquid over a wide temperature range, good heat-transferproperties over a wide range of temperatures), but which have a muchshorter atmospheric lifetime and lower GWPs.

In some embodiments, the acyclic fluorinated compound of the presentdisclosure may exhibit properties that render them particularly usefulas heat transfer fluids for the electronics industry. For example, theacyclic fluorinated compound may be chemically inert (i.e., they do noteasily react with base, acid, water, etc.), and may have high boilingpoints (up to 300° C.), low freezing points (the acyclic fluorinatedcompound may be liquid at −40° C. or lower), low viscosity, high thermalstability, good thermal conductivity, adequate solvency for a range ofpotentially important solutes, and low toxicity. The acyclic fluorinatedcompound of the present disclosure may also, surprisingly, be liquid atroom temperature (e.g., between 20 and 25° C.).

Further, in one embodiment, the compounds of the present disclosure canbe readily prepared in high yield via low cost starting materials. Thestarting materials can be readily purchased or derived fromelectrochemical fluorination. Thus, the compounds described in thepresent disclosure represent a new class of useful and potentially lowcost fluorinated fluids that offer potential advantages in a variety ofapplications including heat transfer, cleaning, and electrolyteapplications.

The acyclic fluorinated compound of the present disclosure (hereinreferred to interchangeably as a compound of the present disclosure) areof the general formula (I)

where:

X is selected from F or CF₃, and Y is selected from H, F, or CF₃,wherein (a) both X and Y are F, (b) X is CF₃ then Y is F, or (c) when Yis CF₃ then X is F;

each R_(f) ¹ is independently selected from a linear or branchedperfluorinated alkyl group comprising 1-8 carbon atoms and optionallycomprising at least one catenated atom selected from O, N, orcombinations thereof; or the two R_(f) ¹ groups are bonded together toform a fluorinated ring structure comprising 4-8 carbon atoms andoptionally comprising at least one catenated atom selected from O, N, orcombinations thereof;

each R_(h) is independently H or CH₃;

A is selected from F, or CF₃ and Z is selected from H, F or CF₃; and

Q is selected from a F atom, a Cl atom, a linear, cyclic, or branchedperfluorinated alkyl group comprising 1-8 carbon atoms and optionallycomprising at least one catenated atom selected from O, N, orcombinations thereof, or a G(R_(f) ²)_(e) group, where G is an O atom ora N atom wherein:

when Q is a Cl atom, then Z and A are F atoms;

when G is O then e is 1, Z is H, F, or CF₃; A is F; and R_(f) ² is alinear or branched perfluorinated alkyl group comprising 1-10 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof;

when G is N then e is 2, and each R_(f) ² group is independently alinear or branched perfluorinated alkyl group comprising 1-8 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof; or the two R_(f) ² groups are bondedtogether to form a fluorinated ring structure comprising 4-8 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof with the proviso that when A is CF₃then Z is F, and when Z is CF₃ then A is F.

As used herein, an acyclic ether refers to a compound, wherein the etheroxygen atom is not contained within a cyclic ring, thus the oxygen atomshown in Formula (I) above is an acyclic ether.

In one embodiment, Q is linear, cyclic, or branched perfluorinated alkylgroup comprising 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms and optionallycomprising at least one catenated atom selected from O, N, orcombinations thereof. In one embodiment, Q is also N(R_(f) ¹)₂.

In one embodiment, Q comprises a perfluorinated morpholine group

Disclosed herein are exemplary compounds of the present disclosure.

In one embodiment, the amine-containing acyclic hydrofluoroethers of thepresent disclosure comprise a substituted diethyl ether. Suchamine-containing acyclic hydrofluoroethers include:

-   -   where (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   where (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   where (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   where (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   where (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   where (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   -   wherein (R_(f) ¹)₂N is selected from:

-   -   -   wherein OR_(f) ² is selected from:

-   -   -   wherein (R_(f) ¹)₂N is selected from:

-   -   -   wherein OR_(f) ² is selected from:

-   -   -   wherein (R_(f) ¹)₂N is selected from:

-   -   -   wherein OR_(f) ² is selected from:

In one embodiment, the amine-containing acyclic hydrofluoroethers of thepresent disclosure comprise a substituted dimethyl ether. Suchamine-containing acyclic hydrofluoroethers include:

-   -   wherein (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   wherein (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   wherein (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   wherein (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   wherein (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   wherein (R_(f) ¹)₂N and (R_(f) ²)₂N are independently selected        from:

-   -   -   wherein (R_(f) ¹)₂N is selected from:

-   -   -   wherein OR_(f) ² is selected from:

-   -   -   wherein (R_(f) ¹)₂N is selected from:

-   -   -   wherein OR_(f) ² is selected from:

-   -   -   wherein (R_(f) ¹)₂N is selected from:

-   -   -   wherein OR_(f) ² is selected from:

Exemplary amine-containing acyclic hydrofluoroethers include:

where “Me” refers to a methyl (—CH₃) group.

The compounds of the present disclosure have good environmentalproperties as well as having good performance attributes, such asnon-flammability, chemical inertness, high thermal stability, goodsolvency, etc.

In one embodiment, the compound of the present disclosure may have a lowenvironmental impact. In this regard, the compounds of the presentdisclosure may have a global warming potential (GWP) of less than 100,50, or even 10. As used herein, GWP is a relative measure of the globalwarming potential of a compound based on the structure of the compound.The GWP of a compound, as defined by the Intergovernmental Panel onClimate Change (IPCC) in 1990 and updated in 2007, is calculated as thewarming due to the release of 1 kilogram of a compound relative to thewarming due to the release of 1 kilogram of CO₂ over a specifiedintegration time horizon (ITH).

${{GWP}_{i}\left( t^{\prime} \right)} = {\frac{\int_{0}^{ITH}{{a_{i}\left\lbrack {C(t)} \right\rbrack}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\left\lbrack {C_{{CO}_{2}}(t)} \right\rbrack}{dt}}} = \frac{{\int_{0}^{ITH}{a_{i}C_{oi}e}} - {{t/\tau_{i}}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\left\lbrack {C_{{CO}_{2}}(t)} \right\rbrack}{dt}}}}$

In this equation a, is the radiative forcing per unit mass increase of acompound in the atmosphere (the change in the flux of radiation throughthe atmosphere due to the IR absorbance of that compound), C is theatmospheric concentration of a compound, τ is the atmospheric lifetimeof a compound, t is time, and i is the compound of interest. Thecommonly accepted ITH is 100 years representing a compromise betweenshort-term effects (20 years) and longer-term effects (500 years orlonger). The concentration of an organic compound, i, in the atmosphereis assumed to follow pseudo first order kinetics (i.e., exponentialdecay). The concentration of CO₂ over that same time intervalincorporates a more complex model for the exchange and removal of CO₂from the atmosphere (the Bern carbon cycle model).

In one embodiment, the compounds of the present disclosure haveatmospheric lifetime of less than 1 year, 0.5 years, or even less than0.1 years.

Non-flammability can be assessed by using standard methods such as ASTMD-3278-96 e-1, D56-05 “Standard Test Method for Flash Point of Liquidsby Small Scale Closed-Cup Apparatus”. In one embodiment, the compound ofthe present disclosure is non-flammable based on closed-cup flashpointtesting following ASTM D-327-96 e-1.

In one embodiment, the compound of the present disclosure isnon-bioaccumulative in animal tissues. For example, some compounds ofthe present disclosure may provide low log K_(ow) values, indicating areduced tendency to bioaccumulate in animal tissues, where K_(ow) is theoctanol/water partition coefficient, which is defined as the ratio ofthe given compound's concentration in a two-phase system comprising anoctanol phase and an aqueous phase. In one embodiment, the log K_(ow)value is less than 7, 6, 5, or even 4.

In one embodiment, the compound of the present disclosure is expected toprovide low acute toxicity based on 4 hour acute inhalation or oraltoxicity studies in rats following U.S. EPA “Health Effects TestGuidelines OPPTS 870.1100 Acute Oral Toxicity” and/or OECD Test No. 436“Acute Inhalation Toxicity-Acute Toxic Class Method”. For example, acompound of the present disclosure has a single dose oral median lethaldose (LD 50) in male and female Sprague-Dawley rats of greater than 30,50, 100, 200, or even 300 mg/kg.

The useful liquid range of a compound of the present disclosure isbetween its pour point and its boiling point. A pour point is the lowesttemperature at which the compound is still able to be poured. The pourpoint can be determined, for example, by ASTM D 97-16 “Standard TestMethod for Pour Point of Petroleum Products”. In one embodiment, thecompound of the present disclosure has a pour point of less than 0° C.,−20° C., −40° C. or even −60° C. In one embodiment, the compound of thepresent disclosure has a boiling point of at least 100° C., 150° C.,200° C., 250° C. or even 300° C.

In some embodiments, the compound of the present disclosure may behydrophobic, relatively chemically unreactive, and thermally stable.

In some embodiments, the compound of the present disclosure may beprepared by free radical addition of acyclic ethers to fluorinatedolefins, a chemistry which has been described by Chambers et al. in J.Chem. Soc. Perkin Trans 1, 1985, p. 2215-2218.

The acyclic fluorinated compound of formula (I) may be prepared from alinear or branched acyclic ether and an amine-containing fluorinatedolefin as described below.

In one embodiment, the acyclic ethers are selected from: dimethyl ether,methyl ethyl ether, diethyl ether, cyclopentyl methyl ether, andisopropyl methyl ether. The fluorinated olefin comprises a terminal orinternal double bond and at least one olefinic C—F bond. In oneembodiment, the fluorinated olefin is perfluorinated. Exemplaryamine-containing fluorinated olefins include: fluorinated vinyl amineand fluorinated 1- and 2-propenyl amines.

Fluorinated vinyl amine and fluorinated propenyl amine compounds can beprepared by electrochemical perfluorination of the appropriatenitrogen-containing hydrocarbon carboxylate derivatives followed bydecarboxylation of the perfluorinated nitrogen-containing carboxylatesusing procedures that are known in the art. Specifically, thefluorinated vinyl amines, 1-propenyl amines, and 2-propenyl amines usedin an exemplary preparation of compositions of the general formula I,can be prepared by synthetic procedures known in the art. See forexample, U.S. Pat. No. 4,985,556 (Abe et al.).

An illustrative, low cost route for the preparation of theamine-containing fluorinated olefins (including fluorinated vinylamines, 1-propenylamines and 2-propenylamines) involves the followingseries of reactions:

Exemplary perfluorinated vinyl amine and perfluorinated propenyl aminesinclude:

Exemplary fluorinated vinyl amine and fluorinated propenyl aminesinclude:

The mole ratio of the amine-containing fluorinated olefin to the acyclicether may be from 3:1 to 1:6, more preferably 2:1 to 1:3. Depending onthe reactivity of the fluorinated olefin and the mole ratio chosen,monosubstituted or disubstituted products can form. For example, a largeexcess of fluorinated olefin favors the disubstituted product. In otherwords the amine-containing fluorinated olefin reacts with both carbonsadjacent to the ether oxygen atom. In one embodiment, the twofluorinated substituents bonded to the acyclic ether moiety areidentical. In other words, —CFZ—CHA-Q is —CFY—CHX—N(R_(f) ¹)₂.

However, in another embodiment, a non-amine-containing fluorinatedolefin is reacted with the acyclic ether in addition to theamine-containing fluorinated olefin, to provide one substituent bondedto the acyclic ether ring derived from the amine-containing fluorinatedolefin and the another substituent bonded to the acyclic ether ringderived from the non-amine-containing fluorinated olefin. Thesenon-amine-containing fluorinated olefins can provide different chemistryand physical properties to the resulting acyclic fluorinated compoundand/or be less costly to manufacture. Such non-amine-containingfluorinated olefins include: pefluorinated olefins, such astetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, andbromotrifluoroethylene; perfluorinated vinyl ethers, such as perfluoro(methyl vinyl) ether, perfluoro (ethyl vinyl) ether, perfluoro (n-propylvinyl) ether, perfluoro-2-propoxypropylvinyl ether,perfluoro-3-methoxy-n-propylvinyl ether, perfluoro-2-methoxy-ethylvinylether, perfluoro-methoxy-methylvinyl ether (CF₃—O—CF₂—O—CF═CF₂),perfluoro-4,8-dioxa-1-nonene (i.e., CF₂═CFO(CF₂)₃OCF₃),C₃F₇—O—CF(CF₃)CF₂—O—CF═CF₂, andCF₃—(CF₂)₂—O—CF(CF₃)—CF₂—O—CF(CF₃)—CF₂—O—CF═CF₂; perfluorinated allylethers, such as perfluoro (methyl allyl) ether (CF₂═CF—CF₂—O—CF₃),perfluoro (ethyl allyl) ether, perfluoro (n-propyl allyl) ether,perfluoro-2-propoxypropyl allyl ether, perfluoro-3-methoxy-n-propylallylether, perfluoro-2-methoxy-ethyl allyl ether, perfluoro-methoxy-methylallyl ether, and CF₃—(CF₂)₂—O—CF(CF₃)—CF₂—O—CF(CF₃)—CF₂—O—CF₂CF═CF₂;CF₃(CF₂)_(n)OCF═CHF where n is an integer of 0-4, CF₂═CHF, andCF₃CF═CHF. Such non-amine-containing fluorinated olefins arecommercially available or can be synthesized using well known methodsthat have been described in the art.

The non-amine-containing fluorinated olefin and the amine-containingfluorinated olefin may be reacted simultaneously or sequentially withthe acyclic ether. Generally, the mole ratio of the non-amine-containingfluorinated olefin to the acyclic ether may be from 3:1 to 1:6, morepreferably 2:1 to 1:3. Again, depending on the nature of thenon-amine-containing fluorinated olefin and/or its mole ratio, thenon-amine-containing fluorinated olefin may add to one or both sides ofthe acyclic ether. However, in the present disclosure only onenon-amine-containing fluorinated olefin is free-radically added toacyclic ether, alpha to the oxygen atom.

The free radical addition of the fluorinated olefin with the acyclicether is promoted by irradiation or suitable free radical initiatingcompounds including peroxides, peroxyesters, or peroxycarbonates togenerate radicals. Examples of such chemical initiators includetert-amylperoxy-2-ethylhexanoate (available under the trade designation“LUPEROX 575” from Arkema, Crosby, Tex.), lauryl peroxide, tent-butylperoxide, tert-amylperoxy-2-ethylhexyl carbonate, and mixtures thereof.Irradiation sources include those known in the art, for example,ultraviolet radiation, x-ray radiation, and gamma radiation.

In some embodiments, the fluorinated olefin and the acyclic ether areheated along with a free radical initiator at temperatures of greaterthan 50, 100, 125, 150, 160 or even 200° C.; and at most 400, 350° C.,or even 300° C.

In one embodiment, the resulting fluorinated compounds can be purifiedto isolate the desired amine-containing acyclic hydrofluoroether.Purification can be done by conventional means including distillation,absorption, extraction, chromatography and recrystallization. Thepurification can be done to isolate the compound of the presentdisclosure (in all of its stereoisomeric forms) from impurities, such asstarting materials, byproducts, etc. The term “purified form” as usedherein means the compound of the present disclosure is at least 90, 95,98, or even 99 wt. % pure.

The compounds of the present disclosure may be used as a working fluidin a variety of applications. The working fluids may include at least25%, 50%, 70%, 80%, 90%, 95%, 99%, or even 100% by weight of theabove-described formula (I) compounds based on the total weight of theworking fluid. In addition to the compounds of the present disclosure,the working fluids may include a total of up to 75%, up to 50%, up to30%, up to 20%, up to 10%, or up to 5% by weight of one or more of thefollowing components: alcohols, ethers, alkanes, alkenes, haloalkenes,perfluorocarbons, perfluorinated tertiary amines, perfluoroethers,cycloalkanes, esters, ketones, oxiranes, aromatics, siloxanes,unsaturated hydrochlorocarbons, unsaturated hydrochlorofluorocarbons,unsaturated hydrofluorocarbons, non-hetero atom-containinghydrofluoroolefins, hydrochloroolefins, hydrochlorofluoroolefins,unsaturated hydrofluoroethers, or mixtures thereof, based on the totalweight of the working fluid. Such additional components can be chosen tomodify or enhance the properties of a composition for a particular use.

In one embodiment, the working fluid has no flash point (as measured,for example, following ASTM D-3278-96 e-1).

In one embodiment, the compound of the present disclosure may be used inan apparatus for heat transfer that includes a device and a mechanismfor transferring heat to or from the device. The mechanism fortransferring heat may include a heat transfer working fluid thatincludes a compound of formula (I) of the present disclosure.

The provided apparatus for heat transfer may include a device. Thedevice may be a component, work-piece, assembly, etc. to be cooled,heated or maintained at a predetermined temperature or temperaturerange. Such devices include electrical components, mechanical componentsand optical components. Examples of devices of the present disclosureinclude, but are not limited to microprocessors, wafers used tomanufacture semiconductor devices, power control semiconductors,electrical distribution switch gear, power transformers, circuit boards,multi-chip modules, packaged and unpackaged semiconductor devices,lasers, chemical reactors, fuel cells, and electrochemical cells. Insome embodiments, the device can include a chiller, a heater, or acombination thereof.

In yet other embodiments, the devices can include electronic devices,such as processors, including microprocessors. As these electronicdevices become more powerful, the amount of heat generated per unit timeincreases. Therefore, the mechanism of heat transfer plays an importantrole in processor performance. The heat-transfer fluid typically hasgood heat transfer performance, good electrical compatibility (even ifused in “indirect contact” applications such as those employing coldplates), as well as low toxicity, low (or non-) flammability and lowenvironmental impact. Good electrical compatibility suggests that theheat-transfer fluid candidate exhibit high dielectric strength, highvolume resistivity, and poor solvency for polar materials. Additionally,the heat-transfer fluid should exhibit good mechanical compatibility,that is, it should not affect typical materials of construction in anadverse manner.

The provided apparatus may include a mechanism for transferring heat.The mechanism may include a heat transfer fluid. The heat transfer fluidmay include one or more compounds of the present disclosure. Heat may betransferred by placing the heat transfer mechanism in thermal contactwith the device. The heat transfer mechanism, when placed in thermalcontact with the device, removes heat from the device or provides heatto the device, or maintains the device at a selected temperature ortemperature range. The direction of heat flow (from device or to device)is determined by the relative temperature difference between the deviceand the heat transfer mechanism.

The heat transfer mechanism may include facilities for managing theheat-transfer fluid, including, but not limited to pumps, valves, fluidcontainment systems, pressure control systems, condensers, heatexchangers, heat sources, heat sinks, refrigeration systems, activetemperature control systems, and passive temperature control systems.Examples of suitable heat transfer mechanisms include, but are notlimited to, temperature controlled wafer chucks in plasma enhancedchemical vapor deposition (PECVD) tools, temperature-controlled testheads for die performance testing, temperature-controlled work zoneswithin semiconductor process equipment, thermal shock test bath liquidreservoirs, and constant temperature baths. In some systems, such asetchers, ashers, PECVD chambers, vapor phase soldering devices, andthermal shock testers, the upper desired operating temperature may be ashigh as 170° C., as high as 200° C., or even as high as 230° C.

Heat can be transferred by placing the heat transfer mechanism inthermal contact with the device. The heat transfer mechanism, whenplaced in thermal contact with the device, removes heat from the deviceor provides heat to the device, or maintains the device at a selectedtemperature or temperature range. The direction of heat flow (fromdevice or to device) is determined by the relative temperaturedifference between the device and the heat transfer mechanism. Theprovided apparatus can also include refrigeration systems, coolingsystems, testing equipment and machining equipment. In some embodiments,the provided apparatus can be a constant temperature bath or a thermalshock test bath. In some systems, such as etchers, ashers, PECVDchambers, vapor phase soldering devices, and thermal shock testers, theupper desired operating temperature may be as high as 170° C., as highas 200° C., 250 C or even higher.

In some embodiments, the compounds of the present disclosure may be usedas a heat transfer agent for use in vapor phase soldering. In using thecompounds of the present disclosure in vapor phase soldering, theprocess described in, for example, U.S. Pat. No. 5,104,034 (Hansen) canbe used, which description is hereby incorporated by reference. Briefly,such process includes immersing a component to be soldered in a body ofvapor comprising at least an acyclic fluorinated compound of the presentdisclosure to melt the solder. In carrying out such a process, a liquidpool of the acyclic fluorinated compound (or working fluid that includesthe acyclic fluorinated compound) is heated to boiling in a tank to forma saturated vapor in the space between the boiling liquid and acondensing means.

A workpiece to be soldered is immersed in the vapor (at a temperature ofgreater than 170° C., greater than 200° C., greater than 230° C., 250 C,or even greater), whereby the vapor is condensed on the surface of theworkpiece so as to melt and reflow the solder. Finally, the solderedworkpiece is then removed from the space containing the vapor.

In another embodiment, the compound of the present disclosure is used inan apparatus for converting thermal energy into mechanical energy in aRankine cycle. The apparatus may include a working fluid that includesone or more compounds of formula (I). The apparatus may further includea heat source to vaporize the working fluid and form a vaporized workingfluid, a turbine through which the vaporized working fluid is passedthereby converting thermal energy into mechanical energy, a condenser tocool the vaporized working fluid after it is passed through the turbine,and a pump to recirculate the working fluid.

In some embodiments, the present disclosure relates to a process forconverting thermal energy into mechanical energy in a Rankine cycle. Theprocess may include using a heat source to vaporize a working fluid thatincludes one or more compounds of formula (I) to form a vaporizedworking fluid. In some embodiments, the heat is transferred from theheat source to the working fluid in an evaporator or boiler. Thevaporized working fluid may pressurized and can be used to do work byexpansion. The heat source can be of any form such as from fossil fuels,e.g., oil, coal, or natural gas. Additionally, in some embodiments, theheat source can come from nuclear power, solar power, or fuel cells. Inother embodiments, the heat can be “waste heat” from other heat transfersystems that would otherwise be lost to the atmosphere. The “wasteheat,” in some embodiments, can be heat that is recovered from a secondRankine cycle system from the condenser or other cooling device in thesecond Rankine cycle.

An additional source of “waste heat” can be found at landfills wheremethane gas is flared off. In order to prevent methane gas from enteringthe environment and thus contributing to global warming, the methane gasgenerated by the landfills can be burned by way of “flares” producingcarbon dioxide and water which are both less harmful to the environmentin terms of global warming potential than methane. Other sources of“waste heat” that can be useful in the provided processes are geothermalsources and heat from other types of engines such as gas turbine enginesthat give off significant heat in their exhaust gases and to coolingliquids such as water and lubricants.

In the provided process, the vaporized working fluid may expanded thougha device that can convert the pressurized working fluid into mechanicalenergy. In some embodiments, the vaporized working fluid is expandedthrough a turbine which can cause a shaft to rotate from the pressure ofthe vaporized working fluid expanding. The turbine can then be used todo mechanical work such as, in some embodiments, operate a generator,thus generating electricity. In other embodiments, the turbine can beused to drive belts, wheels, gears, or other devices that can transfermechanical work or energy for use in attached or linked devices.

After the vaporized working fluid has been converted to mechanicalenergy the vaporized (and now expanded) working fluid can be condensedusing a cooling source to liquefy for reuse. The heat released by thecondenser can be used for other purposes including being recycled intothe same or another Rankine cycle system, thus saving energy. Finally,the condensed working fluid can be pumped by way of a pump back into theboiler or evaporator for reuse in a closed system.

The desired thermodynamic characteristics of organic Rankine cycleworking fluids are well known to those of ordinary skill and arediscussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274(Zyhowski et al.). The greater the difference between the temperature ofthe heat source and the temperature of the condensed liquid or aprovided heat sink after condensation, the higher the Rankine cyclethermodynamic efficiency. The thermodynamic efficiency is influenced bymatching the working fluid to the heat source temperature. The closerthe evaporating temperature of the working fluid to the sourcetemperature, the higher the efficiency of the system. Toluene can beused, for example, in the temperature range of 79° C. to about 260° C.,however toluene has toxicological and flammability concerns. Fluids suchas 1,1-dichloro-2,2,2-trifluoroethane and 1,1,1,3,3-pentafluoropropanecan be used in this temperature range as an alternative. But1,1-dichloro-2,2,2-trifluoroethane can form toxic compounds below 300°C. and need to be limited to an evaporating temperature of about 93° C.to about 121° C. Thus, there is a desire for otherenvironmentally-friendly Rankine cycle working fluids with highercritical temperatures so that source temperatures such as gas turbineand internal combustion engine exhaust can be better matched to theworking fluid.

In one embodiment, the compound of the present disclosure is used in acleaning compositions along with one or more co-solvents. In someembodiments, the present disclosure relates to a process for cleaning asubstrate. The cleaning process can be carried out by contacting acontaminated substrate with a cleaning composition. The compound of thepresent disclosure can be utilized alone or in admixture with each otheror with other commonly-used cleaning co-solvents. Representativeexamples of co-solvents which can be used in the cleaning compositioninclude methanol, ethanol, isopropanol, t-butyl alcohol, methyl t-butylether, methyl t-amyl ether, 1,2-dimethoxyethane, cyclohexane,2,2,4-trimethylpentane, n-decane, terpenes (e.g., a-pinene, camphene,and limonene), trans-1,2-dichloroethylene, cis-1,2-dichloroethylene,methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethylacetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone,naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene,bis(trifluoromethyl)benzenes, hexamethyl disiloxane, octamethyltrisiloxane, perfluorohexane, perfluoroheptane, perfluorooctane,perfluorotributylamine, perfluoro-N-methyl morpholine, perfluoro-2-butyloxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane,1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane,1,1,1,2,2-pentafluoro-3,3-dichloropropane,1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane,1,1,1,2,2,4-hexafluorobutane,1-trifluoromethyl-1,2,2-trifluorocyclobutane,3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane,or mixtures thereof. Such co-solvents can be chosen to modify or enhancethe solvency properties of a cleaning composition for a particular useand can be utilized in ratios (of co-solvent to compounds according toformula (I)) such that the resulting composition has no flash point. Ifdesirable for a particular application, the cleaning composition canfurther contain one or more dissolved or dispersed gaseous, liquid, orsolid additives (for example, carbon dioxide gas, surfactants,stabilizers, antioxidants, or activated carbon).

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more compounds of the presentdisclosure and optionally one or more surfactants. Suitable surfactantsinclude those surfactants that are sufficiently soluble in the compoundof the present disclosure, and which promote soil removal by dissolving,dispersing or displacing the soil. One useful class of surfactants arethose nonionic surfactants that have a hydrophilic-lipophilic balance(HLB) value of less than about 14. Examples include ethoxylatedalcohols, ethoxylated alkylphenols, ethoxylated fatty acids, alkylarylsulfonates, glycerol esters, ethoxylated fluoroalcohols, and fluorinatedsulfonamides. Mixtures of surfactants having complementary propertiesmay be used in which one surfactant is added to the cleaning compositionto promote oily soil removal and another added to promote water-solublesoil removal. The surfactant, if used, can be added in an amountsufficient to promote soil removal. Typically, surfactant may be addedin amounts from 0.1 to 5.0 wt. % or from 0.2 to 2.0 wt. % of thecleaning composition.

The cleaning compositions can be used in either the gaseous or theliquid state (or both), and any of known or future techniques for“contacting” a substrate can be utilized. For example, a liquid cleaningcomposition can be sprayed or brushed onto the substrate, a gaseouscleaning composition can be blown across the substrate, or the substratecan be immersed in either a gaseous or a liquid composition. Elevatedtemperatures, ultrasonic energy, and/or agitation can be used tofacilitate the cleaning. Various different solvent cleaning techniquesare described by B. N. Ellis in Cleaning and Contamination ofElectronics Components and Assemblies, Electrochemical PublicationsLimited, Ayr, Scotland, pages 182-94 (1986).

Both organic and inorganic substrates can be cleaned by the processes ofthe present disclosure. Representative examples of the substratesinclude metals; ceramics; glass; polycarbonate; polystyrene;acrylonitrile-butadiene-styrene copolymer; natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool; synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof; fabrics comprising a blend of natural andsynthetic fibers; and composites of the foregoing materials. In someembodiments, the process may be used in the precision cleaning ofelectronic components (e.g., circuit boards), optical or magnetic media,or medical devices.

In still another embodiment, the compound of the present disclosure isused in a dielectric fluids, which can be used in electrical devices(e.g., capacitors, switchgear, transformers, or electric cables orbuses). For purposes of the present application, the term “dielectricfluid” is inclusive of both liquid dielectrics and gaseous dielectrics.The physical state of the fluid, gaseous or liquid, is determined at theoperating conditions of temperature and pressure of the electricaldevice in which it is used.

In some embodiments, the dielectric fluids include one or more compoundsof formula (I) and, optionally, one or more second dielectric fluids.Suitable second dielectric fluids include, for example, air, nitrogen,helium, argon, and carbon dioxide, or combinations thereof. The seconddielectric fluid may be a non-condensable gas or an inert gas.Generally, the second dielectric fluid may be used in amounts such thatvapor pressure is at least 70 kPa at 25° C., or at the operatingtemperature of the electrical device.

The dielectric fluids of the present application comprising thecompounds of formula (I) are useful for electrical insulation and forarc quenching and current interruption equipment used in thetransmission and distribution of electrical energy. Generally, there arethree major types of electrical devices in which the fluids of thepresent disclosure can be used: (1) gas-insulated circuit breakers andcurrent-interruption equipment, (2) gas-insulated transmission lines,and (3) gas-insulated transformers. Such gas-insulated equipment is amajor component of power transmission and distribution systems.

In some embodiments, the present disclosure provides electrical devices,such as capacitors, comprising metal electrodes spaced from each othersuch that the gaseous dielectric fills the space between the electrodes.The interior space of the electrical device may also comprise areservoir of the liquid dielectric fluid which is in equilibrium withthe gaseous dielectric fluid. Thus, the reservoir may replenish anylosses of the dielectric fluid.

In another embodiment, the present disclosure relates to coatingcompositions comprising (a) a solvent composition that includes one ormore compounds of the present disclosure, and (b) one or more coatingmaterials which are soluble or dispersible in the solvent composition.

In various embodiments, the coating materials of the coatingcompositions may include pigments, lubricants, stabilizers, adhesives,anti-oxidants, dyes, polymers, pharmaceuticals, release agents,inorganic oxides, and the like, and combinations thereof. For example,coating materials may include unsaturated perfluoropolyether,unsaturated hydrocarbon, and silicone lubricants; amorphous copolymersof tetrafluoroethylene; polytetrafluoroethylene; or combinationsthereof. Further examples of suitable coating materials include titaniumdioxide, iron oxides, magnesium oxide, unsaturated perfluoropolyethers,polysiloxanes, stearic acid, acrylic adhesives, polytetrafluoroethylene,amorphous copolymers of tetrafluoroethylene, or combinations thereof.

In some embodiments, the above-described coating compositions can beuseful in coating deposition, where the compounds of Formula (I)function as a carrier for a coating material to enable deposition of thematerial on the surface of a substrate. In this regard, the presentdisclosure further relates to a process for depositing a coating on asubstrate surface using the coating composition. The process comprisesthe step of applying to at least a portion of at least one surface of asubstrate a coating of a liquid coating composition comprising (a) asolvent composition containing one or more of the compounds of formula(I); and (b) one or more coating materials which are soluble ordispersible in the solvent composition. The solvent composition canfurther comprise one or more co-dispersants or co-solvents and/or one ormore additives (e.g., surfactants, coloring agents, stabilizers,anti-oxidants, flame retardants, and the like). Preferably, the processfurther comprises the step of removing the solvent composition from thecoating by, e.g., allowing evaporation (which can be aided by theapplication of, e.g., heat or vacuum).

In various embodiments, to form a coating composition, the components ofthe coating composition (i.e., the compound(s) of formula (I), thecoating material(s), and any co-dispersant(s) or co-solvent(s) utilized)can be combined by any conventional mixing technique used fordissolving, dispersing, or emulsifying coating materials, e.g., bymechanical agitation, ultrasonic agitation, manual agitation, and thelike. The solvent composition and the coating material(s) can becombined in any ratio depending upon the desired thickness of thecoating. For example, the coating material(s) may constitute from about0.1 to about 10 weight percent of the coating composition.

In illustrative embodiments, the deposition process of the disclosurecan be carried out by applying the coating composition to a substrate byany conventional technique. For example, the composition can be brushedor sprayed (e.g., as an aerosol) onto the substrate, or the substratecan be spin-coated. In some embodiments, the substrate may be coated byimmersion in the composition. Immersion can be carried out at anysuitable temperature and can be maintained for any convenient length oftime. If the substrate is a tubing, such as a catheter, and it isdesired to ensure that the composition coats the lumen wall, thecomposition may be drawn into the lumen by the application of reducedpressure.

In various embodiments, after a coating is applied to a substrate, thesolvent composition can be removed from the coating (e.g., byevaporation). If desired, the rate of evaporation can be accelerated byapplication of reduced pressure or mild heat. The coating can be of anyconvenient thickness, and, in practice, the thickness will be determinedby such factors as the viscosity of the coating material, thetemperature at which the coating is applied, and the rate of withdrawal(if immersion is utilized).

Both organic and inorganic substrates can be coated by the processes ofthe present disclosure. Representative examples of the substratesinclude metals, ceramics, glass, polycarbonate, polystyrene,acrylonitrile-butadiene-styrene copolymer, natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool, synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof, fabrics including a blend of natural andsynthetic fibers, and composites of the foregoing materials. In someembodiments, substrates that may be coated include, for example,magnetic hard disks or electrical connectors with perfluoropolyetherlubricants or medical devices with silicone lubricants.

In some embodiments, the present disclosure further relates toelectrolyte compositions that include one or more compounds of thepresent disclosure. The electrolyte compositions may comprise (a) asolvent composition including one or more of the compounds according toformula (I); and (b) at least one electrolyte salt. The electrolytecompositions of the present disclosure exhibit excellent oxidativestability, and when used in high voltage electrochemical cells (such asrechargeable lithium ion batteries) provide outstanding cycle life andcalendar life. For example, when such electrolyte compositions are usedin an electrochemical cell with a graphitized carbon electrode, theelectrolytes provide stable cycling to a maximum charge voltage of atleast 4.5V and up to 6.0V vs. Li/Li⁺.

Electrolyte salts that are suitable for use in preparing the electrolytecompositions of the present disclosure include those salts that compriseat least one cation and at least one weakly coordinating anion (theconjugate acid of the anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid (for example, PF₆ ⁻ anion or abis(perfluoroalkanesulfonyl)imide anion); that are at least partiallysoluble in a selected compound of formula (I) (or in a blend thereofwith one or more other compounds of formula (I) or one or moreconventional electrolyte solvents); and that at least partiallydissociate to form a conductive electrolyte composition. The salts maybe stable over a range of operating voltages, are non-corrosive, and maybe thermally and hydrolytically stable. Suitable cations include alkalimetal, alkaline earth metal, Group IIB metal, Group IIIB metal,transition metal, rare earth metal, and ammonium (for example,tetraalkylammonium or trialkylammonium) cations, as well as a proton. Insome embodiments, cations for battery use include alkali metal andalkaline earth metal cations. Suitable anions includefluorine-containing inorganic anions such as (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻,AsF₆ ⁻, and SbF₆ ⁻; CIO₄ ⁻; HSO₄ ⁻; H₂PO₄ ⁻; organic anions such asalkane, aryl, and alkaryl sulfonates; fluorine-containing andnonfluorinated tetraarylborates; carboranes and halogen-, alkyl-, orhaloalkylsubstituted carborane anions including metallocarborane anions;and fluorine-containing organic anions such asperfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,(perfluoroalkanesulfonyl)imides, bis(perfluoroalkanesulfonyl)methides,and tris(perfluoroalkanesulfonyl)methides; and the like. Preferredanions for battery use include fluorine-containing inorganic anions (forexample, (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, and AsF₆ ⁻) and fluorine-containingorganic anions (for example, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides). The fluorine-containing organicanions can be either fully fluorinated, that is perfluorinated, orpartially fluorinated (within the organic portion thereof). In someembodiments, the fluorine-containing organic anion is at least about 80percent fluorinated (that is, at least about 80 percent of thecarbon-bonded substituents of the anion are fluorine atoms). In someembodiments, the anion is perfluorinated. The anions, including theperfluorinated anions, can contain one or more catenary heteroatoms suchas, for example, nitrogen, oxygen, or sulfur. In some embodiments,fluorine-containing organic anions include perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides.

In some embodiments, the electrolyte salts may include lithium salts.Suitable lithium salts include, for example, lithiumhexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithiumbis(perfluoroethanesulfonyl)imide, lithium tetrafluoroborate, lithiumperchlorate, lithium hexafluoroarsenate, lithiumtrifluoromethanesulfonate, lithiumtris(trifluoromethanesulfonyl)methide, lithium bis(fluorosulfonyl)imide(Li—FSI), and mixtures of two or more thereof.

The electrolyte compositions of the present disclosure can be preparedby combining at least one electrolyte salt and a solvent compositionincluding at least one compound of formula (I), such that the salt is atleast partially dissolved in the solvent composition at the desiredoperating temperature. The compounds of the present disclosure (or anormally liquid composition including, consisting, or consistingessentially thereof) can be used in such preparation.

In some embodiments, the electrolyte salt is employed in the electrolytecomposition at a concentration such that the conductivity of theelectrolyte composition is at or near its maximum value (typically, forexample, at a Li molar concentration of around 0.1-4.0 M, or 1.0-2.0 M,for electrolytes for lithium batteries), although a wide range of otherconcentrations may also be employed.

In some embodiments, one or more conventional electrolyte solvents aremixed with the compound(s) of formula (I) (for example, such that thecompound(s) of formula (I) constitute from about 1 to about 80 or 90percent of the resulting solvent composition). Useful conventionalelectrolyte solvents include, for example, organic andfluorine-containing electrolyte solvents (for example, propylenecarbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate,ethyl methyl carbonate, dimethoxyethane, 7-butyrolactone, diglyme (thatis, diethylene glycol dimethyl ether), tetraglyme (that is,tetraethylene glycol dimethyl ether), monofluoroethylene carbonate,vinylene carbonate, ethyl acetate, methyl butyrate, tetrahydrofuran,alkyl-substituted tetrahydrofuran, 1,3-dioxolane, alkyl-substituted1,3-dioxolane, tetrahydropyran, alkyl-substituted tetrahydropyran, andthe like, and mixtures thereof). Other conventional electrolyteadditives (for example, a surfactant) can also be present, if desired.

The present disclosure further relates to electrochemical cells (e.g.,fuel cells, batteries, capacitors, electrochromic windows) that includethe above-described electrolyte compositions. Such an electrochemicalcell may include a positive electrode, a negative electrode, aseparator, and the above-described electrolyte composition.

A variety of negative and positive electrodes may be employed in theelectrochemical cells. Representative negative electrodes includegraphitic carbons e.g., those having a spacing between (002)crystallographic planes, d₀₀₂, of 3.45 A>d₀₀₂>3.354 A and existing informs such as powders, flakes, fibers or spheres (e.g., mesocarbonmicrobeads); Li_(4/3)Ti_(5/3)0₄ the lithium alloy compositions describedin U.S. Pat. No. 6,203,944 (Turner et al.) and U.S. Pat. No. 6,255,017(Turner); and combinations thereof. Representative positive electrodesinclude LiFePO₄, LiMnPO₄, LiCoPO₄, LiMn₂O₄, LiCoO₂ and combinationsthereof. The negative or positive electrode may contain additives suchas will be familiar to those skilled in the art, e.g., carbon black fornegative electrodes and carbon black, flake graphite and the like forpositive electrodes.

The electrochemical devices of the present disclosure can be used invarious electronic articles such as computers, power tools, automobiles,telecommunication devices, and the like.

Exemplary embodiments of the present disclosure include, but should notbe limited to, the following:

Embodiment 1. A acyclic fluorinated compound of formula (I)

where:

each R_(h) is independently H or CH₃;

X is selected from F or CF₃, and Y is selected from H, F, or CF₃,wherein when X is CF₃ then Y is F and when Y is CF₃ then X is F;

each R_(f) ¹ is independently selected from a linear or branchedperfluorinated alkyl group comprising 1-8 carbon atoms and optionallycomprising at least one catenated atom selected from O, N, orcombinations thereof; or the two R_(f) ¹ groups are bonded together toform a fluorinated ring structure comprising 4-8 carbon atoms andoptionally comprising at least one catenated atom selected from O, N, orcombinations thereof;

A is selected from F, or CF₃;

Z is selected from H, F or CF₃; and

Q is selected from (i) a F atom, (ii) a Cl atom, (iii) a linear, cyclic,or branched perfluorinated alkyl group comprising 1-8 carbon atoms andoptionally comprising at least one catenated atom selected from O, N, orcombinations thereof, or (iv) a G(R_(f) ²)_(e) group, where G is an Oatom or a N atom wherein:

when Q is a Cl atom, then Z and A are F atoms;

when G is O then e is 1, Z is H, F or CF₃; A is F; and R_(f) ² is alinear or branched perfluorinated alkyl group comprising 1-10 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof;

when G is N then e is 2, and each R_(f) ² group is independently alinear or branched perfluorinated alkyl group comprising 1-8 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof or the two R_(f) ² groups are bondedtogether to form a fluorinated ring structure comprising 4-8 carbonatoms and optionally comprising at least one catenated atom selectedfrom O, N, or combinations thereof, with the proviso that when A is CF₃then Z is F, and when Z is CF₃ then A is F.

Embodiment 2. The acyclic fluorinated compound of embodiment 1, whereinQ=N(R_(f) ¹)₂.

Embodiment 3. The acyclic fluorinated compound of any one of theprevious embodiments, wherein N(R_(f) ¹)₂ is a perfluorinated morpholinegroup.

Embodiment 4. The acyclic fluorinated compound of embodiment 1, whereinQ is a perfluorinated alkyl group comprising less than 4 carbon atoms.

Embodiment 5. The acyclic fluorinated compound of any one of theprevious embodiments, wherein X and Y are both F.

Embodiment 6. The acyclic fluorinated compound of any one of theprevious embodiments, wherein A and Z are both F.

Embodiment 7. The acyclic fluorinated compound of any one of theprevious embodiments, wherein the unsaturated fluorinated compoundcomprises at least one of the following:

where Me refers to a methyl group.

Embodiment 8. The acyclic fluorinated compound of any one of theprevious embodiments, wherein the acyclic fluorinated compound isnonflammable based on closed-cup flashpoint testing following ASTMD-327-96 e-1.

Embodiment 9. The acyclic fluorinated compound of any one of theprevious embodiments, wherein the acyclic fluorinated compound has aglobal warming potential of less than 100.

Embodiment 10. The acyclic fluorinated compound of any one of theprevious embodiments, wherein the acyclic fluorinated compound isnonflammable based on closed-cup flashpoint testing following ASTMD-327-96 e-1.

Embodiment 11. The acyclic fluorinated compound of any one of theprevious embodiments, wherein the acyclic fluorinated compound has aglobal warming potential of less than 100.

Embodiment 12. A working fluid comprising the acyclic fluorinatedcompound according to any one of the previous embodiments, wherein theacyclic fluorinated compound is present in the working fluid in anamount of at least 25% by weight based on the total weight of theworking fluid.

Embodiment 13. The working fluid of embodiment 12, wherein the workingfluid further comprises a co-solvent.

Embodiment 14. Use of the acyclic fluorinated compound of any oneembodiments 1-11, wherein the acyclic fluorinated compound is in acleaning composition.

Embodiment 15. Use of the acyclic fluorinated compound of any oneembodiments 1-11, wherein the acyclic fluorinated compound is anelectrolyte solvent or additive.

Embodiment 16. Use of the acyclic fluorinated compound of any oneembodiments 1-11, wherein the acyclic fluorinated compound is a heattransfer fluid.

Embodiment 17. Use of the acyclic fluorinated compound of any oneembodiments 1-11, wherein the acyclic fluorinated compound is a vaporphase soldering fluid.

Embodiment 18. An apparatus for heat transfer comprising:

a device; and

a mechanism for transferring heat to or from the device, the mechanismcomprising a heat transfer fluid that comprises the acyclic fluorinatedcompound according to any one of embodiments 1-11.

Embodiment 19. An apparatus for heat transfer according to embodiment18, wherein the device is selected from a microprocessor, asemiconductor wafer used to manufacture a semiconductor device, a powercontrol semiconductor, an electrochemical cell, an electricaldistribution switch gear, a power transformer, a circuit board, amulti-chip module, a packaged or unpackaged semiconductor device, a fuelcell, and a laser.

Embodiment 20. An apparatus according to any one of embodiments 18-19,wherein the mechanism for transferring heat is a component in a systemfor maintaining a temperature or temperature range of an electronicdevice.

Embodiment 21. An apparatus according to any one of embodiments 18-20,wherein the device comprises an electronic component to be soldered.

Embodiment 22. An apparatus according to any one of embodiments 18-21,wherein the mechanism comprises vapor phase soldering.

Embodiment 23. A method of transferring heat comprising:

providing a device; and

transferring heat to or from the device using a heat transfer fluid thatcomprises a acyclic fluorinated compound according to any one ofembodiments 1-11.

Embodiment 24. A composition comprising a purified form of the acyclicfluorinated compound according to any one of embodiments 1-11.

EXAMPLES

Unless otherwise noted, all parts, percentages, ratios, etc. in theexamples and the rest of the specification are by weight, and allreagents used in the examples were obtained, or are available, fromgeneral chemical suppliers such as, for example, Sigma-Aldrich Corp.,Saint Louis, Mo., or may be synthesized by conventional methods.

The following abbreviations are used in this section: mL=milliliter,min=minutes, h=hours, g=gram, mol=mole, mmol=millimole.

The following abbreviations are used in this section: mL=milliliter,min=minutes, h=hours, g=gram, kPa=kilopascal, psi=pounds per squareinch, mol=mole, mmol=millimole, GC=gas chromatography, GC-MS=gaschromatography-mass spectrometry.

TABLE 1 Materials List Material Description Diethyl ether Commerciallyavailable from Sigma-Aldrich Corp. Dimethyl ether Commercially availablefrom Sigma-Aldrich Corp. tert-Butanol Commercially available fromSigma-Aldrich Corp. TAPEH tert-Amylperoxy-2-ethylhexanoate, available asLUPEROX 575 from Arkema, Crosby, TX. HFP Hexafluoropropene, commerciallyavailable from Sigma-Aldrich Corp. tBuOOtBu tert-Butyl peroxide,commercially available from Sigma-Aldrich Corp. MVA2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2- trifluorovinyl)morpholine, whichmay be synthesized by the methods described in Abe et al. Chem. Lett.1988, 1887-1890; Abe et al. Chem. Lett. 1989, 905-908. Pf vinylpyrrolidine 2,2,3,3,4,4,5,5-octafluoro-1-(1,2,2-trifluorovinyl)pyrrolidine, which may be synthesized by the methodsdescribed in Abe et al. Chem. Lett. 1988, 1887-1890; Abe et al. Chem.Lett. 1989, 905-908. Pf N-Et-N-(1-2,2,3,3,5,5,6,6-octafluoro-1-(perfluoroethyl)- propenyl)piperazine4-(perfluoroprop-1-en-1-yl)piperazine, which may be synthesized by themethods described in Abe et al. Chem. Lett. 1988, 1887-1890; Abe et al.Chem. Lett. 1989, 905-908. M-1P2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1- en-1-yl)morpholine, whichmay be synthesized by the methods described in Abe et al. Chem. Lett.1988, 1887-1890; Abe et al. Chem. Lett. 1989, 905-908.

Example 1(EX-1) Preparation of4-(3-ethoxy-1,2,2-trifluorobutyl)-2,2,3,3,5,5,6,6-octafluoromorpholineand4,4′-(oxybis(1,2,2-trifluorobutane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine)

A 600 mL Parr reactor was charged with diethyl ether (51.1 g, 689 mmol),MVA (50.2 g, 161 mmol), and TAPEH (3.2 g, 14 mmol). The reactor was thensealed and the resultant mixture was slowly heated to 75° C. After a 16h stir, the reaction mixture was heated to 90° C. followed by a 0.5 hstir to consume any remaining initiator. After cooling to roomtemperature, GC analysis of the crude reaction material indicated 99%conversion of the MVA starting material. Single-plate distillationafforded4-(3-ethoxy-1,2,2-trifluorobutyl)-2,2,3,3,5,5,6,6-octafluoromorpholine(143° C. at ambient pressure, 24.8 g, 40%) and4,4′-(oxybis(1,2,2-trifluorobutane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine)(143° C., 1.0 torr, 27.8 g, 25%). Analysis by GC-MS confirmed thepresence of formation of4-(3-ethoxy-1,2,2-trifluorobutyl)-2,2,3,3,5,5,6,6-octafluoromorpholineand4,4′-(oxybis(1,2,2-trifluorobutane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine).

Example 2(EX-2) Preparation of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-3-methoxypropyl)morpholineand4,4′-(oxybis(1,2,2-trifluoropropane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine)

To a cooled (dry ice/acetone bath) 600 mL Parr reactor containing MVA(46.8 g, 150 mmol), TAPEH (2.0 g, 8.7 mmol), and tert-butanol (44.3 g,598 mmol) was added dimethyl ether (39.8 g, 864 mmol). The reactor wasthen sealed and the resultant mixture was slowly heated to 75° C. Aftera 16 h stir, the reaction mixture was heated to 90° C. followed by a 0.5h stir to consume any remaining initiator. After cooling to roomtemperature, the crude reaction mixture was washed with water (50 mL).The fluorous phase was collected and GC analysis indicated 65%conversion of the MVA starting material. Single-plate distillationafforded2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-3-methoxypropyl)morpholine(142° C. at ambient pressure, 9.3 g, 17%) and4,4′-(oxybis(1,2,2-trifluoropropane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine)(91° C., 0.3 ton, 20.1 g, 20%). Analysis by GC-MS confirmed theformation of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-3-methoxypropyl)morpholineand4,4′-(oxybis(1,2,2-trifluoropropane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine).

Example 3(EX-3) Preparation of2,2,3,3,4,4,5,5-octafluoro-1-(1,2,2-trifluoro-3-(2,2,3,4,4,4-hexafluorobutoxy)propyl)pyrrolidine

To a cooled (dry ice/acetone bath) 600 mL Parr reactor containingdimethyl ether (51.6 g, 1.12 mol) and TAPEH (5.5 g, 24 mmol) was slowlyadded hexafluoropropene (HFP, 28.6 g, 191 mmol). The internal reactiontemperature was allowed to slowly rise to room temperature and was thenslowly heated to 50° C. The internal pressure reached 1.38×10³ kPa (200psi). After a 16 h stir at the same temperature, the pressure dropped to965 kPa (140 psi). The reactor was then heated to 80° C. and stirred for0.5 h to consume any remaining initiator. After cooling to roomtemperature, the crude reaction material was purified via single-platedistillation to afford 1,1,1,2,3,3-hexafluoro-4-methoxybutane (80.6° C.at ambient pressure, 31.6 g, 85%).

A 300 mL Parr reactor was charged with1,1,1,2,3,3-hexafluoro-4-methoxybutane (10.5 g, 53.5 mmol), Pf vinylpyrrolidine (16.4 g, 55.6 mmol), and tBuOOtBu (0.6 g, 4.0 mmol). Thereactor was then sealed and the resultant mixture was slowly heated to125° C. After a 16 h stir, the reaction mixture was heated to 160° C.followed by a 0.5 h stir to consume any remaining initiator. Aftercooling to room temperature, GC analysis indicated 3% conversion of the1,1,1,2,3,3-hexafluoro-4-methoxybutane starting material to2,2,3,3,4,4,5,5-octafluoro-1-(1,2,2-trifluoro-3-(2,2,3,4,4,4-hexafluorobutoxy)propyl)pyrrolidine.Analysis by GC-MS confirmed the formation of2,2,3,3,4,4,5,5-octafluoro-1-(1,2,2-trifluoro-3-(2,2,3,4,4,4-hexafluorobutoxy)propyl)pyrrolidine.

Example 4(EX-4) Preparation of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-3-((3,3,4,5,5,5-hexafluoropentan-2-yl)oxy)butyl)morpholine

A 600 mL Parr reactor was charged with diethyl ether (110 g, 1.5 mol)and TAPEH (4.3 g, 18.8 mmol). The reactor was sealed and heated to 75°C. followed by the slow addition of HFP (56.3 g, 375 mmol). Aftercomplete addition of HFP, the mixture was allowed to stir for 16 hbefore heating to 90° C. to consume any remaining initiator (TAPEH).After 0.5 h, the reaction mixture was allowed to cool to roomtemperature. The resultant crude reaction mixture was subjected tosingle plate distillation (115° C. at ambient pressure) to afford4-ethoxy-1,1,1,2,3,3-hexafluoropentane (22.5 g, 27%) as a colorlessliquid.

A 300 mL Parr reactor was charged with4-Ethoxy-1,1,1,2,3,3-hexafluoropentane (10.1 g, 45.1 mmol), MVA (14.4 g,46.3 mmol), and tBuOOtBu (0.6 g, 4.0 mmol). The reactor was then sealedand the resultant mixture was slowly heated to 125° C. After a 16 hstir, the reaction mixture was heated to 160° C. followed by a 0.5 hstir to consume any remaining initiator. After cooling to roomtemperature, GC analysis indicated 4.5% conversion of the4-Ethoxy-1,1,1,2,3,3-hexafluoropentane starting material to2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-3-((3,3,4,5,5,5-hexafluoropentan-2-yl)oxy)butyl)morpholine.Analysis by GC-MS confirmed the formation of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-3-((3,3,4,5,5,5-hexafluoropentan-2-yl)oxy)butyl)morpholine.

Example 5(EX-5) Preparation of4-(3-ethoxy-1,2-difluoro-2-(trifluoromethyl)butyl)-2,2,3,3,5,5,6,6-octafluoromorpholineand4,4′-(oxybis(1,2-difluoro-2-(trifluoromethyl)butane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine)

To a 600 mL Parr reactor was charged diethyl ether (60.4 g, 815 mmol),M-1P (73.5 g, 204 mmol), and TAPEH (4.1 g, 18 mmol). The reactor wasthen sealed and the resultant mixture was slowly heated to 75° C. Aftera 16 h stir, the reaction mixture was heated to 90° C. followed by a 0.5h stir to consume any remaining initiator. After cooling to roomtemperature, GC analysis of the crude reaction material indicated 35%conversion of the M-1P starting material and a product ratio of 1:14-(3-ethoxy-1,2-difluoro-2-(trifluoromethyl)butyl)-2,2,3,3,5,5,6,6-octafluoromorpholine:4,4′-(oxybis(1,2-difluoro-2-(trifluoromethyl)butane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine).Analysis by GC-MS confirmed the formation of4-(3-ethoxy-1,2-difluoro-2-(trifluoromethyl)butyl)-2,2,3,3,5,5,6,6-octafluoromorpholineand4,4′-(oxybis(1,2-difluoro-2-(trifluoromethyl)butane-3,1-diyl))bis(2,2,3,3,5,5,6,6-octafluoromorpholine)

Foreseeable modifications and alterations of this invention will beapparent to those skilled in the art without departing from the scopeand spirit of this invention. This invention should not be restricted tothe embodiments that are set forth in this application for illustrativepurposes. To the extent that there is any conflict or discrepancybetween this specification as written and the disclosure in any documentmentioned or incorporated by reference herein, this specification aswritten will prevail.

What is claimed is:
 1. A acyclic fluorinated compound of formula (I)

where: each R_(h) is independently H or CH₃; X is selected from F orCF₃, and Y is selected from H, F, or CF₃, wherein when X is CF₃then Y isF and when Y is CF₃then X is F; each R_(f) ¹ is independently selectedfrom a linear or branched perfluorinated alkyl group comprising 1-8carbon atoms and optionally comprising at least one catenated atomselected from O, N, or combinations thereof; or the two R_(f) ¹ groupsare bonded together to form a fluorinated ring structure comprising 4-8carbon atoms and optionally comprising at least one catenated atomselected from O, N, or combinations thereof; A is selected from F, orCF₃; Z is selected from H, F or CF₃; and Q is selected from (i) a Fatom, (ii) a Cl atom, (iii) a linear, cyclic, or branched perfluorinatedalkyl group comprising 1-8 carbon atoms and optionally comprising atleast one catenated atom selected from O, N, or combinations thereof, or(iv) a G(R_(f) ²)_(e) group, where G is an O atom or a N atom wherein:when Q is a Cl atom, then Z and A are F atoms; when G is O then e is 1,Z is H, F or CF₃; A is F; and R_(f) ² is a linear or branchedperfluorinated alkyl group comprising 1-10 carbon atoms and optionallycomprising at least one catenated atom selected from O, N, orcombinations thereof; when G is N then e is 2, and each R_(f) ² group isindependently a linear or branched perfluorinated alkyl group comprising1-8 carbon atoms and optionally comprising at least one catenated atomselected from O, N, or combinations thereof or the two R_(f) ² groupsare bonded together to form a fluorinated ring structure comprising 4-8carbon atoms and optionally comprising at least one catenated atomselected from O, N, or combinations thereof, with the proviso that whenA is CF₃ then Z is F, and when Z is CF₃ then A is F.
 2. The acyclicfluorinated compound of claim 1, wherein Q =N(R_(f) ¹)₂.
 3. The acyclicfluorinated compound of claim 2, wherein N(R_(f) ¹)₂ is a perfluorinatedmorpholine group.
 4. The acyclic fluorinated compound of claim 1,wherein Q is a perfluorinated alkyl group comprising less than 4 carbonatoms.
 5. The acyclic fluorinated compound of claim 1, wherein X and Yare both F.
 6. The acyclic fluorinated compound of claim 1, wherein Aand Z are both F.
 7. The acyclic fluorinated compound of claim 1,wherein the acyclic fluorinated compound comprises at least one of thefollowing:

where Me refers to a methyl group.
 8. A working fluid comprising theacyclic fluorinated compound according to claim 1, wherein the acyclicfluorinated compound is present in the working fluid in an amount of atleast 25% by weight based on the total weight of the working fluid.
 9. Acomposition comprising a purified form of the acyclic fluorinatedcompound according to claim
 1. 10. The acyclic fluorinated compound ofclaim 1, wherein the acyclic fluorinated compound has a global warmingpotential of less than
 100. 11. A working fluid comprising the acyclicfluorinated compound according to claim 1, wherein the acyclicfluorinated compound is present in the working fluid in an amount of atleast 25% by weight based on the total weight of the working fluid. 12.The working fluid of claim 11, wherein the working fluid furthercomprises a co-solvent.
 13. An apparatus for heat transfer comprising amechanism for transferring heat to or from a device, the mechanismcomprising a heat transfer fluid that comprises the acyclic fluorinatedcompound according to claim
 1. 14. An apparatus for heat transferaccording to claim 13, wherein the device is selected from amicroprocessor, a semiconductor wafer used to manufacture asemiconductor device, a power control semiconductor, an electrochemicalcell, an electrical distribution switch gear, a power transformer, acircuit board, a multi-chip module, a packaged or unpackagedsemiconductor device, a fuel cell, and a laser.
 15. An apparatusaccording to claim 13, wherein the mechanism for transferring heat is acomponent in a system for maintaining a temperature or temperature rangeof an electronic device.
 16. An apparatus according to claim 13, whereinthe device comprises a soldered electronic component.
 17. An apparatusaccording to claim 13, wherein the mechanism comprises vapor phasesoldering.